汽油氧化重整制氢反应过程研究
摘要
本论文的目的是研制开发以汽油为原料的经济、方便的质子交换膜燃料电池(PEMFC)的氢源。
首先运用数学的方法确定了汽油氧化重整制氢复杂反应体系的独立反应方程数，并对反应体系进行了热力学分析与计算。影响体系的重要因素依次为氧油比、水碳比及反应压力等。计算确定了不同反应温度条件下的最佳氧油比和水碳比。
制备、筛选并评价了汽油氧化重整制氢反应催化剂，研制出具有高活性、高选择性及耐热抗氧稳定性良好的催化剂。
本论文系统地考察了操作条件如反应温度、氧油比、水碳比及空速对汽油氧化重整制氢反应的影响。固定床反应器中操作条件考察实验结果表明，汽油氧化重整制氢反应的最佳操作条件是：温度700～800℃、氧油比0.5～2.0、水碳比1.5～2.5、空速为500～5000h~(-1)及常压的条件下进行。
首次在Ni-Pd/Al_2O_3催化剂上对汽油氧化重整制氢反应的本征动力学和宏观动力学进行了详细的实验研究，建立了经验的动力学方程，工程检验结果表明建立的动力学方程是适用的。
催化剂效率因子的计算结果表明内扩散对汽油氧化重整制氢反应过程影响较大，且内扩散影响随着反应温度的增加而增加。
建立了汽油氧化重整制氢反应的非等温活塞流基础模型，探索了工艺条件、反应器工艺参数等对汽油氧化重整制氢反应行为的影响，对适合于汽油氧化重整制氢反应器的设计、反应器最佳工艺参数的确定具有指导意义。
This paper is to develop the economic and convenient hydrogen source from partial oxidation and steam reforming gasoline for the proton exchange membrane fuel cell (PEMFC).
The independent equations have been ascertained for the reaction system of partial oxidation and steam reforming of gasoline by using mathematical method. The reaction system has been thermodynamically analyzed and calculated. The important order factors of effecting on the system are molar ratios of oxygen to oil, water to carbon and pressure, respectively. The optimum ratios of oxygen to oil and water to carbon have been confirmed based on calculation at different reaction temperatures. The minimum ratio of water to carbon that avoids the carbon formation has been confirmed.
The catalyst of partial oxidation and steam reforming of gasoline to produce hydrogen has been first prepared, which has higher activity, selectivity, heat-resistant and better stability.
The effect of technologic conditions such as reaction temperature, molar ratios of oxygen to oil and water to carbon on the partial oxidation and steam reforming of gasoline has been investigated in the fixed-bed reactor. According to the fixed-bed reactor results, it showed that the optimum conditions for the partial oxidation and steam reforming of gasoline were as follows: 700~800C, 0.5~2.0 molar ratio of
oxygen to oil, 1.5~2.5 molar ratio of water to carbon and 500~5000h-1 space velocity. The macro and intrinsical kinetics for the partial oxidation and steam reforming of gasoline has been first detailedly investigated. The experiential equations have been established based on experiment. The engineering test results showed that the experiential equations were appropriate.
The calculation results of catalyst efficient factor showed that the catalyst inner diffusibility had great effect on the partial oxidation and steam reforming of gasoline, which was serious with the increasing reaction temperature.
The non-isothermal plunger flow model for the partial oxidation and steam reforming of gasoline has been established. The effect of technologic conditions and reactor parameters on the partial oxidation and steam reforming of gasoline has been analyzed based on the model, which was useful for the designing reactor and optimizing the reactor parameters.
首先运用数学的方法确定了汽油氧化重整制氢复杂反应体系的独立反应方程数，并对反应体系进行了热力学分析与计算。影响体系的重要因素依次为氧油比、水碳比及反应压力等。计算确定了不同反应温度条件下的最佳氧油比和水碳比。
制备、筛选并评价了汽油氧化重整制氢反应催化剂，研制出具有高活性、高选择性及耐热抗氧稳定性良好的催化剂。
本论文系统地考察了操作条件如反应温度、氧油比、水碳比及空速对汽油氧化重整制氢反应的影响。固定床反应器中操作条件考察实验结果表明，汽油氧化重整制氢反应的最佳操作条件是：温度700～800℃、氧油比0.5～2.0、水碳比1.5～2.5、空速为500～5000h~(-1)及常压的条件下进行。
首次在Ni-Pd/Al_2O_3催化剂上对汽油氧化重整制氢反应的本征动力学和宏观动力学进行了详细的实验研究，建立了经验的动力学方程，工程检验结果表明建立的动力学方程是适用的。
催化剂效率因子的计算结果表明内扩散对汽油氧化重整制氢反应过程影响较大，且内扩散影响随着反应温度的增加而增加。
建立了汽油氧化重整制氢反应的非等温活塞流基础模型，探索了工艺条件、反应器工艺参数等对汽油氧化重整制氢反应行为的影响，对适合于汽油氧化重整制氢反应器的设计、反应器最佳工艺参数的确定具有指导意义。
This paper is to develop the economic and convenient hydrogen source from partial oxidation and steam reforming gasoline for the proton exchange membrane fuel cell (PEMFC).
The independent equations have been ascertained for the reaction system of partial oxidation and steam reforming of gasoline by using mathematical method. The reaction system has been thermodynamically analyzed and calculated. The important order factors of effecting on the system are molar ratios of oxygen to oil, water to carbon and pressure, respectively. The optimum ratios of oxygen to oil and water to carbon have been confirmed based on calculation at different reaction temperatures. The minimum ratio of water to carbon that avoids the carbon formation has been confirmed.
The catalyst of partial oxidation and steam reforming of gasoline to produce hydrogen has been first prepared, which has higher activity, selectivity, heat-resistant and better stability.
The effect of technologic conditions such as reaction temperature, molar ratios of oxygen to oil and water to carbon on the partial oxidation and steam reforming of gasoline has been investigated in the fixed-bed reactor. According to the fixed-bed reactor results, it showed that the optimum conditions for the partial oxidation and steam reforming of gasoline were as follows: 700~800C, 0.5~2.0 molar ratio of
oxygen to oil, 1.5~2.5 molar ratio of water to carbon and 500~5000h-1 space velocity. The macro and intrinsical kinetics for the partial oxidation and steam reforming of gasoline has been first detailedly investigated. The experiential equations have been established based on experiment. The engineering test results showed that the experiential equations were appropriate.
The calculation results of catalyst efficient factor showed that the catalyst inner diffusibility had great effect on the partial oxidation and steam reforming of gasoline, which was serious with the increasing reaction temperature.
The non-isothermal plunger flow model for the partial oxidation and steam reforming of gasoline has been established. The effect of technologic conditions and reactor parameters on the partial oxidation and steam reforming of gasoline has been analyzed based on the model, which was useful for the designing reactor and optimizing the reactor parameters.
引文
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